Liquid treatment



j ent d'M r 29 945 t v 1 ."JAbraham Sidney,Behrman, Chicago, and Hilding 1 B. jGustaf'son, La Grange, Ill.',,-'assignors to h I Infilco Incorporated, a corporation of Delaware h NoDra'wing. Application September 11, 1939, v V "Seriall\To.294,288- v 3 Claims. (ci. 2101-23) This invention relates a to l the treatment of liquids, and isconcerned particularly with new i and improved methods for the removalrof unde slrable impurities from water and other aqueous liquids. i

p More especially,- the invention directedto improvements in the method of removing silica and fluorine-from water by means ofmagnesium'hydroxide precipitated-.inqthe, waten,

y As'is nowwellknown, the presence offluorine I in excess of 1,0 part per'million is highly obiectionable inapotable,watersupply since fluorine in such quantities has been shown definitely to he responsible for endemic dental fiuorosis, more.

commonly known as mottled ,toothisenamelfl It is likewise well knownthat the presence ofsilica fineness of a fewparts per million is highly undesirabe-in the feedrwatersu'pply of modernhigh pressure boilers in which rapid and unimpeded heat transfer is imperative, due to the hazard of a the formation of azsiliceousgscaleon, the boiler tubes which is such an efiective thermal insulator 1 that -local=overheating and failure of the tubes may readily resultu v It was shown by Scott and his associates: (J our- ,nal American Water Works.;Association,,.volumea, 9

'lli

of course suflicientexcess of the dolorniticlime is employed to provide the proper quantity-of cal- ,ciumhydroxide foryprecipitation of the magnesium, The; additiomof ordinary magne'sum I hydroxide to thewater to be treated is to be dise tinguished from the processor thev applicants in whichmagnesium carbonate is used, as more fully described hereafter'r such magnesium carbonate :Ueither'being previously prepared orprepared in lsitu by, first adding magnesium oxide or bydroxide and then treating with carbon dioxide to .form .a magnesium'carbonate of increased activity. i

e Unfortunately, howevergthe'ladditionoflilag- 'nesium sulfate or chloride to a water for increasing the completeness of silica or fluorine-removal in the treated water.

' of adsorption phenomena, ingeneral, the ,added increases also'theamount of sulfates or chlorides Since, as. is characteristic magnesium required is an exponential and not a linear, functioncf the amountsof silica or fluorine to be removed, disproportionately-jlargedosages ,:pages 9,-25, 1937) that fluorinepinmagnesiumfor the purpose, a further reduction of the fluorine increased amount, of magnesiummydroxide on subsequent lime treatment.

. containingwaterscould be reduced by. softening the uwater with limejtc precipitatemagnesium ci hydroxide which apparently'adsorbs the;fiuorine; and that, if the-amount of magnesium compounds originally present, in the water was not: suflicient ofradded magnesium. fililiate or chloride are re-' quired for progressivelymore completeremoval.

In consequence, particularly--11; the caseiof silica .removal, the amount of: salts.; (usually-sodium salts) addedtoa boiler feed-water;inthis-way I i 1! maybe sQ-greatas tog-be an appreciable factor in boilerplant operation',,as,f orexample by increasing-the frequency or amountlof boilerblowdown a required t permit reasonably; satisfactory boiler operation.- It should be borne -in mindgthat for I satisfactory silica lremovalit maybe-necessary content couldbe accomplishedbyadding asoluble s magnesium compound (such' asythe-sulfate or chloride) to the water toxform a correspondingly t quse dosages of magnesium' sulfate.,(Epsom salts) of as highas'5Ito20 grains pengallon, just as is the caselwith the current popular employ- ..ment ofanhydrous jferrlc sulfate. v

magnesium'sulfate, per. gallonfwill-add to awater i It has also-beenfoundthat silica in 'WstKmay likewise be ,removedyby magnesium hydroxide precipitatedinthe watr.)Hereagain itis posadding an appropriate-amount oi larsoluble mag nesiurn salt such as magnesium sulfate" to the U I I water before precipitation ;of the magnesium hydroxidel after softening onlyajlittle more than half as 7 much sodium sulfatezas'will be producedby 1'.

. grainof anhydrous ferricsulfatathequantlty besible to increase the degre'e of, silica removal by It is of interest-tonote that wehave found that for effective silicairemoval it isnecessary'to form -the magnesiuni;hydroxide in:situ', that is,;in the water being treated;:and that contact withjpreviously formed soli'd particles of ordinarymagnesium hydroxide'isinefiective; Thus,

- .101 example, treatment of a given water with .dolomitic lime, which,-' in .wateniorms magnesium hydrox'ide instead of the usual high calcium lime accompiishes no greater silica removal, even though comes animportant consideraticim inboileropera- ,tion, especially when-highdosagesof magnesium sulfate are required. 1 1t;shou1d;be noted also that i any magnesiumsulfate (-orgchloride) added. to the 5 water will require f the employment of both lime r; and sodaeash for uprecipitation" and softening, thus furtherincreasing theicostuof ,water treatvmenttothatextent',

the amount or soluble sulfates (or chlorides, nitrates, etcJQadded to a *wateras a result of the.addition of rnagnesium We have discovered-that sulfate (or chloride, nitrate, etc .');;-:for thespurpose described can be eliminated completely by adding magnesium to the water in the form of the While. 1 grain carbonate'f'or bicarbonate. When subsequently the water is treated with lime for the precipitaj -tionoi magnesium hydroxide, the carbonate or f bicarbonate, ion of ti1e magnesium compound is g likewise precipitated as calcium carbonate; thus 5 leavingno soluble salts remaining in the water r completeness of silica removal. f

. l ams possible-every oi treatment r g y i r g lllfepreier to use magnesiumcarbonate instead o1 the-bicarbonate as far as the solubility oi the carbonate will "permit; since thebicarbonate requires-twice'as 'much lime as the carbonate for 1 as a result of mistreatment, Since this is true creased for the purpose of improved fluorineremoval from a community water supplinthe lack i I W of any increase in the, amount of solublesalts 1 1 accruing irom the employment otimagnesiu m 1 Y carbonate for ;bicarbonate' is also -'very advanta- *geous sincethe large amount'of suliates or chlofor the precipitationof magnesium-hydroxide,

'whereas in'the-case'of-magneslum'suliate orchloride both lii'nefand"soda-ashlor their equivalent o! sodium hydroxide) must'be'added-ior the pre- 3 cipitatio'n "and softening reactions. *Theuse or 40' magnesium' carbonate or bicarbonate therefore in'arkedeconomyin the cost the the precipitatiorilofione u'nitoi: magnesium.

calcium emanate. v

' v -Most"ofjthe 1'nethod's-wehaveifound suitable Tfor addingmag'nesium carbonateor bicarbonate a the watei to beitre'ated 'depend'on the general principle of treating a solid alkaline: magnesium I i 1 "compound with a solution-oi carbon dioxide. in a preferred method is to 'carbon dioxide from cohvenient'sourc'e to the-water tobetreated andthen pass the water througha'bed-oi=magnesiu'rn oxide or carbonate. calcinedfmagnesite hasbeeni'oundiquit'e satisfactory, both physically and chemicalli fas has alsof 'thef-granular "fac- -tivated fmagnesiaf? I now available commercially; I since the solidoxide-"(or hydroxidm-is present in excess, normal magnesium carbonate is the'prin- "'cipal producti'resultingi'iroin tnegacuomot the carbon dioicide'. Neither uncalcined" magnesite' v1" magnesiunrcarbonate)? nor dolomite has been found very satisi'actory, due to the comparative -lackoi reactivity oi' these materials towards 'carbon 'dioxidefiturthermore, at least; a substantial if r j palrt'of 'th'e magne'sium carbonate dissolved would j.

i present as the bicarbonate; requiring Jgtwice as mu'c'hlimei as the normalfcar bonate obtained from f thefoxide. Differentially calcinedidolomite may 3 alsqibefiitilizd that is, do1omitewhich'has been -calc'ined' at a temperature sufficiently high to decompose the magnesium carbonate-,but-not-the regardless of the amount-of; magnesium carbonate; 1dr bicarbonateithat mayhave been added tothe I waterfjitfollows that as large 'anfaddition of mag iiesiu'm as desired may be madeto the, wateri fthat is, of course, within the limits of solubility "of magnesium carbonate and bicarbonate with- I outfearlof increasingthe' amouhtofdissolved-i' salts in the treated .vvatenqv .-It thus becomes tease ible for the first time to addfas tnuchmag'nesiumto "the water as is; required; f to fg'i ve the desired when the magnesium contentoiawaterjis in: I

v 5 "'ridesf added-"te the water' 11' magnesium sulfate.

-' for chloride had beenutilized: can. impart a dis agreeable tasteitothejwatenespeciallyin those cases-wherethe' waterlmayhave had an appreciable initiallslilfate and chloride content.- 3

Another important advantage' i resulting from the. employment or 'magnesium carbonate-or bi- 3 carbonateasa sourceoi addedmagnesium is that V I lime-only need be used-jin subsequent treatment the alkaline magnesium compound, it is possible to carbonate a suspension of more finely divided 7 material. Where feasible, for example, one may carbonate a suitable sludge from a previous lime treatment. It. has been found that magnesium hydroxide canbe separatedirom calcium'car bonate'in the mixed sludge by treatment with carbon dioxide. provided that the magnesium hydroidde is present in excess andlthatisufllcient .time oi contact is provided to permit theattainment of equilibrium.

fWhere flue sflses or 'other combustion gases are employed as a source of carbondiox'lde, the'maximum concentration of carbon dioxide that can {be obtained bycontacting these gases'with water is of the'ord'er of 100 to 200 parts per million; due

tothe low Dai' ialpressure-of carbon dioxideLIi .it is desired to use a larger amount or magnesium carbonate or bicarbonate than couldbesecured irom-su'ch concentration or carbon dioxide, the watermay be passed through severalbeds of the alkaline magnesium compound with treatment with the'icombustion gases between each pass; or-'the .;water :maybe circulated several .times with through 1 the bed of" alkaline material, addition of the flue gases during each passii Another alternative procedure fis toflxpass. the com- 1 u bus'tion gasesthrough-thejwater w'hileit' iscon-itact with the calcined magnesiteorother alkaline magnesium compound, thussimultaneously contacting th 'water.with=carbondioxide and the magnesiumzcompoundi- For-examplefthe water may be passed downwardly, and the combustion 8358s =upwardly,'. through a bed" or calcined magnesite,'- the rates of flow oif the -two fluids-being proportioned to give the desired"degreexofi solu- 1 tion oi'thei magnesium compound.'- -,Or, as previously mentioned; a slurryof; the-"lmagnesium" compound maybe treatedfwithl-the combustioni v V .r 3- =1 I A novel method-iorfproviding thecarbon dioxiderequi're d tor the formation of magnesium, carbonate or bicarbo'nate, andone which is high- 7 1y emcient within its proper i held of usefulness, consists essentially in first passing the: raw'water to be treated through a bed ci hydrogen exchange material, such as the carbonaceous 'zeolitesflfcertaintypeset-synthetic resins, or other'products L "now availabiefor this purpose,whereby-theposi- V tivelions oilthe' 'compounds presentiin-"the water;1 f 'are replaced with hydrogen, ,the'treated' :waterf I "thus containingthe corresponding jacid's-et'ypical- 1 ly 'carbonic, sulfuric, and hydrochlori'ca 'Ordina'rip zly,a,-however, fortthe purpose at hand,"=when the -ialkalinity ot the raw water is sufllcient, we prefer to control the hydrogen'exchange sothat, inefiect; only the bicarbonatesare 'co'nvertedto the corresponding acid .-(i. e; carbonic acid) while, the suliates'and chlorides are-not afiected'; for

P;'M.', analkalinity of 390?. P.-M. ahd'ahardness of '368 1?. P.--M.-was subjectedto' hydrogen exchange utreatment and uthen passedgthrou'gh a -:bed of" calcined magnesite, which "increased the phenolphthalein'r alkalinity to 212 P. P. M1 and the methyl-orange alkalinity to 524 P: P, M. When this water was subsequently treated with lime, the characteristics oi--thei treated""-water were as follows: phenolp'hthaiein alkilinity. 54;

P, P. M., methyl-orange alkalinity 76 P. P. M., hardness 88 P. P. M. and silica 2 P. P. M. In a second case, a. water having initialhardness of 59 P. P. M., alkalinity 122 P. P. M., and silica 72 P. P. M. was similar subjected to hydrogen I zeolite treatment and then passed through a bed of calcined magnesite, after which it had a phenolphthalein alkalinity of 120 P. P. M. and methyl-orange alkalinity of 260 P. P. M. On subsequent treatment with lime the silica was reduced o P. P. M. I

Another water, which contained both silica and fluorine in objectionable amount. had an in-' itial hardness of 241 P. P. M., alkalinity 354 P. P. M., silica 64 P. P. M., and fluorine .1.3 P. P. M. After progressive treatment with hydrogen zeolite and with calcined magnesite, the phenolpht-halein alkalinity was 240 P. P. M. and the methylorange alkalinity 568 P. P. M. vOn subsequent treatment with lime to precipitate'the niagcarbonate" as used in the claims includes both nesium, the silica content was reduced to 2 P.'

in the liquid undesirable soluble compounds as.

a result of the treatment. Various modifications and applications of our invention will naturally occur to those skilled in the art. All such ramiflcations of our. invention are contemplated as coming within its scope as defined in the claims. It will be understood that the term magnesium the normal carbonate and the bicarbonate.

, We claim:

1. A process for treating water which comprises subjecting the water successively to hydrogen exchange treatment and thereby producing carbon dioxide in the water, to contact with a body of a. compound taken from the class consisting of magnesium oxide and magnesium hydroxide, thereby producing magnesium carbonate in the water, to. treatment with a hydroxide capable of reacting with the magnesium carbonate to produce magnesium hydroxide for the precipitation of magnesium as magnesium hydroxide, and. separating the precipitated magnesium from the water.

2. A process for'removing from a bicarbonate water impurities of the class consisting of silica and'fluorine which comprises successively producing carbon dioxide in the'water by hydrogen exchange treatment, contacting this water with v the hydrogen exchange is controlled so' as to de-.

compose only bicarbonate without conversion of sulfates and chlorides to free suliuric and hydrochloric acid.

ABRAHAM SIDNEY BEHBMAN. I-HLDING B. GUBTAFSON. 

